Treatment of hydrocarbons



June 4, 1935- w. o. MrrscHERLxNG 2,003,898

TREATMENT' 0F HYDROCARBONS Filed April 28, 1931 I 2 Sheets-Sheet l RARE $45 LAMP frs/pancakes maar June 4, 1935. w. o. MrrscHERLlNG TREATMENT OF HYDROCARBONS 2 Sheets-Sheet 2 Filed April 2.8, 1931 vom @amer @5A/SER INVENTOR WMM/1m? d /l//Uf//f/Pl/A/c.

Patented June 4, 1935 PATENT oFFICE TREATMENT F HYDROCARBONS Waldemar 0. Mtscherling, Bridgeport, Conn., as-

signor to Neon Research of Connecticut, Inc., Bridgeport, Conn., a corporation of Connecticut Application April 28, 1931, Serial No. 533,406

35 Claims.

tached to aryl groups, (hereinafter referred to for brevity as aliphatic hydrocarbon compounds), to form degradation products and/or oxidation products thereof and has as a general object a provision of novel processes and means for accomplishing such treatment in a convenient, ecient and economicial manner. The eX- pressions degradation and degrading as used in the specification and claims denote a depolymerization or simplification of the Ahydrocarbon body or molecule resulting in the formation of a product or products having a less complex molecular structure or lower molecular weight and a lower boiling point.

A further object of the invention is to provide processes and means for such treatment including the subjection of aliphatic hydrocarbons to A the radiations of a rare gas lamp preferably of the vpositive column type such as, for example, a neon tube.

A particular object of the invention is to subject aliphatic hydrocarbons (either pure or mixtures) to the radiations of a rare gas lamp such as a neon lamp, in a manner and for a time sufficient to lower the boiling point of the whole of the material treated or ofa particular portion thereof, and/or simultaneously or alternatively to form oxidation products thereof as desired.

A more specic object of the invention is to provide processes and means for. subjecting such materials to the radiations of a neon lamp in the presence of an oxidizing or reducing catalytic material to form alcohols or ketones therefrom.

A further object of the invention is to provide novel catalytic materials suitable for use as aforesaid.

Other objects of the invention are in part obvious and Will in part appear hereinafter.

The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others, and the apparatus and means embodying features of construction, combinations of elements and arrangement of parts which are adapted to effect such steps, all as exemplified in the following detailed disclosure. The scope of the invention will be indicated in the claims.

For a fuller understanding of the nature and objects of the invention reference should be had to the following detailed description taken in connection with the accompanying drawings, in which:

Fig. 1 shows side elevational view in part diagrammatic showing a simple form of apparatus adapted for continuous treatment of complex aliphatic hydrocarbons to form degradation products thereof;

Fig. 2 is a similar view of a modified form of the apparatus shown in Fig. 1;

Fig. 3 is an elevation view partly in vertical section showing a preferred form of apparatus for accomplishinga treatment similar to that in Fig. 1, but in vapor phase;

Figs. 4 and 5 are perspective views and Fig. 6 is a vertical sectional view, each showing details of construction of the apparatus shown in Fig. 3;

Fig. 7 is a vertical sectional view of an oxidation or reduction apparatus;

Fig. 8 is a vertical sectional view of another form of apparatus suitable for effecting oxidation or reduction.

As indicated in the above brief description of the drawings and as will be readily apparent to one skilled in the art upon reading the more detailed description which follows, the novel processes comprising the present invention contemplate the treatment of aliphatic hydrocarbons, and also contemplates the treatment of these hydrocarbons in either liquid or vapor (including gaseous) phase; and the processes (according to the construction of the apparatus used) may be either of the batch-type or continuous type.

Referring more particularly to the drawings,

kin Fig. 1 is shown a simple embodiment of apparatus in which the rare gas tube I0 of glass or the like containing a rare gas II, (neon, for example), and having electrodes I2 at "each of its ends, attached to a source A. C. potential, and it is surrounded by a non-conducting jacket I3 through which, as the tube I0 is operated, the liquid or vapor to be treated is slowly passed Vby means of an inlet I4 and an outlet I5. Fig. 1 also includes a diagrammatic disclosure of a supply tank I6 containing a material to be treated and a receiving tank I'I for receiving the material aftertreatment; the supply tank I 6 in the embodiment shown containing a complex aliphatic hydrocarbon mixture commonly known as gas oil and having a boiling range of from 200-800 C., and the tank I'I receiving the degradation products of the gas oil the boiling range of which has been reduced by treatment' to 15o-'1oo C., both as indicated by thegures showing the temperature ranges. In Fig. 2 is shown an apparatus identical with the embodiment shown in Fig. 1 except that the jacket I3 is surrounded by a metallic member I8 which, in a preferred form, only partially covers the jacket I3 and is in the form of a coil of lead or the like which is grounded as indicated at I9. When using this form of apparatus I have found that instead of lowering the entire range of the boiling point of gas oil, for

example, the degradation of the hydrocarbons is accomplished largely in the middle range, whereby when the treated material is subjected to an Engler distillation test the curve shows a marked increase in the amount of material boiling between the range of 250 and 300 C.

In Fig. 3 is shown an embodiment of apparatus adapted for continuous treatment of a mixture of aliphatic hydrocarbons, in which there is provided a vessel or column 28 of copper or the like into the bottom of which the oil, for example, is introduced through a spray head 2| at a temperature of about 400 C., and under a pressure of about 70 lbs. attainedy through the medium of a pump 22.

In this column 20 a pressure of about 200 millimeters of mercury is maintained by any suitable means, (not shown) whereby the oil introduced through the spray head 2| is instantly vaporized. Immediately above the' spray head 2I is provided a-double walled plate 22 which is shown in detail in' Fig. 4 and which is provided with a plurality of tubular passages 23 through which the vaporized oil freely passes and which has its upper wall 22' provided with a. plurality of small openings 24 through which moisture supplied at 25 is intimately admixed with the vaporized oil.

Above the plate 22 is situated a lter bed 26 which may be composed of any suitable broken and preferablyv porous material such as, for example, cracked pumice stone, that will serve to strip out or break up any large particles of oil which may tend to rise through the column 20 and to further mix the vapors. If desired, the pumice stone may be impregnated with spongy copper in a manner to be described hereinafter.

Above the filter bed 26 the column 20 is preferably provided with one or more baille plates 21 which are provided with openings and serve further to intimately admix the v'aporized oil and moisture and above these baille plates is located a rare gas tube 28 such as, for example, a neon tube which is preferably in coiled form as shown particularly in Fig. 5. Finally at the top of the column there is preferably provided a heating coil 29 which is kept at a temperature of around 212 C., for example, and serves to prevent an undue amount of reuxing in the column. It will, of course, be apparent that the heating coil 29 maybe otherwise situated for the same purpose or that a plurality of such coils may be used when necessary. When treating a normally gaseous hydrocarbon material the use of such heating coil may be dispensed with. At its top the column 20 is provided with a take-olf pipe which leads to-one or more condensers. As shown, the apparatus is preferably provided with a primary condenser 3| which, when treating gas oil, is maintained at a temperature ofaround 80 C.; anda secondary condenser 32 which is preferably maintained at a temperature of about 14 C. Each of these condensers operate to condense the treated vaporized oil and water and if desired the liquid condensed by the primary condense;` 3l may be taken oil as indicated diagrammatically at 3l' before the residual vapors are passed to the secondary condenser 32.

The liquids condensed in treating gas oil by any of the methods and in any of the apparatus show in Figs. 1 to 3 inclusive may then be distilled and the gasoline fraction recovered therefrom, whereupon the' residue may be cracked for the further production of gasoline by any desired method. By the use of the apparatus in the manner shown the total recovery of Government standard gasoline from gas oil can be increased by as much as 15% or more over that otherwise produced by the same cracking process. The disclosure of the condensers in Fig. 3 is merely for the purpose of simplicity of illustration and it is, of course, to be understood that other means of recovery of the treated products may be used Without departing from the spirit of the invention.

Aliphatic hydrocarbons are, in general, highly inflammable, and in treating them in an apparatus such asV shown i'n Fi'g. Y3, there might be danger of an explosionshould the mixture become ignited either by an accidental spark or s by the cracking or breaking of the neon tube. To eliminate this danger, and to allow for differences in expansion characteristics, the gasket through which the ends of the neon tube 28 pass are preferably constructed as shown in detail in Fig. 6. Aroun'd the neon tube 28 is disposed a glass or porcelain insulator 33 which is enclosed Within a lbushing 34 that screws into or is otherwise suitably joined to the column 20 and closely surrounds the neck of the neon tube 28. Held within the bushing 34 is a` suitable non-conducting viscous mixtureV Vsuch as, for example, a pasty mixture 34' of glycerine and barium sulphate which minimizes leakage of gas about the bushing and into the column 20, and over the entire structure and the end of the neon tube is disposed a gas-tight sheath 35. 'Ihis sheath is initially evacuated and is then lled with nitrogen gas or other inert gas or vapor through an opening 36 which is thereafter continuously attached to a source of such gas as shown at 31. The lead vwire 28 to the electrode of the neon tube, (which is attached to a source of A. C. potential), passes out of the sheath 35 through a suitable insulator 38 and, as will be readily understood by one skilled in the art, as a result of such a construction if any gas leaks into the column 20 it will be an' inert gas and will not form an explosive mixture with the hydrocarbon being treated.

In Fig. 7 is shown an apparatus of the batchtype which is suitable for the treatment of aliphatic hydrocarbon compounds to vproduce products such as alcohols, or keton'es, although it is to be understood that the present invention contemplates also Athe carrying out of such treatment in a continuous type of apparatus. In the embodiment shown thereis provided a container 39 of non-conducting material such as glass or the like in which is placed a foraminous member 40 for holding the'catalyzing material 4I; the member 40 being preferably formed of metallic material such as, for example, nickel. Disposed in the catalyzing material is a U-shaped or coiled rare gas tube 42, such as, for example, a neon tube which is provided with electrodes 43 and a source of A. C. potential, and the container 40 is'lledito a suitable height with the material to be treated. When treating volatile liquid hydrocarbons to produce volatile products such as alcohols, `the container 3B is suitably covered as shown at 44 and is provided with a reflux condenser y45. It is also preferably surrounded by a layer of mercury or other suitable conducting material 46 which is either grounded or has a low potential, for example about 5 volts, applied thereto at points opposed to and adjacent the ends of the neon tube; the neon tube preferably being operated at a high potential as, for example, about 15,000 volts and the polarity of the adjacent electrode of the neon tube being opposite to that of the conducting material. Also, if desired, the metallic holder 40 for the catalyzing material 4I may be grounded or may have a low potential applied thereto at points adjacent the ends of the tube, in which case the polarity should be like that of the adjacent electrodes of the neon ube. l

E desired, the member 46 may be omitted although the apparatus shown isfound to give a more rapid and perhaps a more complete action than it does without the member 46, although it is to be understood that in any case the treatment may be carried on to the degree and for the formation of the compounds desired.

Fig. 8 illustrates another form of apparatus which is suitable for effecting treatment of aliphatic hydrocarbons whether as a batch or asa continuous operation. The apparatus comprises a container 60 which may be of metal or a nonconducting material and having its upper end closed by a cover or cap 6l. The container is provided with an inlet 62 and an outlet or overflow 63, the overflow being so positioned as to maintain the height of a liquid 18 in the bot. tom of the container at a certain predetermined level. This outlet also prevents the liquid from rising to an undue height within the container.

A foraminous holder 64 is preferably positioned near the top of the container and may be constructed of a perforated .metal, as nickel.

The holder may be in theform of an annulus and within the holder is positioned a rare gas tube, as Va neon tube, 65. Within the holder and surrounding the neon tube is a catalytic material 66 which may be either of an oxidizing or a reducing nature, as hereinafter more fully described. Positioned beneath the holder is a collecting chamber 61 .which may preferably be of annular form and is fixedly attached to-the walls of the container as by means of bolts B8 which likewise attach to the walls a supporting member 69 for the holder 64.k Leading from the collecting chamber is avpipe or conduit 10 for the purpose of withdrawing liquid from the collecting chamber. This pipe may be in the form of. and act on the principle of a siphon.

Centrally disposed within the container, positioned within the annular holder 64 and collecting chamber 61 and extending beneath the surface of the liquid 18 is a pump 1l. This pump may be of conical shape as shown, al-

Y though it will be readily understood that other types of pumps may be employed. The pump is mounted upon a shaft 62 passing through an opening 13 in the cover 6| and is actuated by a suitable source of power, as a motor 15. The apex of the cone is provided with an orifice 'l1 and at its greatest circumference the periphery is provided with a number of orifices 16. The cover A el has also an .opening 14 through which the pipe 10 passes. The openings 13 and 16 are nite,

preferably closed. They may, however, be open and when open there may be located with` respect to such openings a suitable means (not shown) for preventing the escape ofvapors as for example, the positioning of `a paddle or propeller immediately adjacent to the opening 13 upon shaft 12. The energyis supplied to the neon tube by means of leads 19.

.Inroperation the hydrocarbon to be treated may be introduced through the inlet 62 until the container is lled to the level of the outlet 63 thereby covering the lower end or orifice 'I1- of the pump. The rapid rotation of the pump 1| causes the liquid to rise along its inner surface. Upon reaching the orifices 16 the liquid is discharged therethrough and passed to, and over the catalytic material and neon tube contained within the holder 64. The treated liquid collects in the chamber 61 beneath the holder and may be Withdrawn therefrom by the conduit 10. The liquid thus withdrawn, if sufciently treated by a single pass, is then ready -either for utilization per se or after rectification to separate it into the desired fractions. However, when the treatment is not sufficient in a single passage of the liquid, it may be repassed, either before or after further processing.

1f the amount of hydrocarbon contacted with the catalyticmaterial is such as to accomplish the desired treatment thereof by a single passage, the process may be made continuous by introducing the hydrocarbon to be vtreated continuously through the inlet 62 at such a `rate as to permit the treatment of the desired amount of hydrocarbon, and for the predetermined overflow through the outlet 63. In the event that the treatment is incomplete by singie contact with the catalyst, the hydrocarbon may be withdrawn from the collecting chamber, and if desired, after separation of certain constituents, returned in a continuous manner to the liquid in the base of the container.

n win be realized, of course, .that the liquid A may be passed to, or contacted with the catalyst and neon tube by means other lthan that particularly shown in the embodiment illustrated in Fig. 8. Thus, the reservoir instead of forming a part of the container may be positioned without this container and the liquid passed to the catalyst by a suitable arrangement of conduits that will be understood by those skilled in the art.

'Ihe catalytic material M '(Fig. '1) and 66 (Fig. 8) may be formed in a variety of ways, the requirements being that it shall be generally granular in form, catalytically active and substantially non-conductive per se, and that it shall contain water and material of an oxidizing or reducing type as desired.

A preferred form of catalytic material may be prepared by treating an active carbon for example, a granular decolorizing carbon such as Darco which is a charcoal having marked absorptive and decolorizing properties and which is prepared by the destructive distillation of carbonaceous material, particularly ligby washing thoroughly; then treating with an organic acid such as acetic acid to form soluble salts with the alkaline mineral constituents thereof; thereafter again washing thoroughly; steaming out the residue of the organic acid; and then impregnating with a solution of an oxidizing substance such as sodium perboate or the like which has preferably been put into colloidal `form by first boiling with a trace of gum such as agar-agar, gum arabic, or

with other suitable materials such as glue,-

glucose or the like. In place of the perborate mentioned, other perborates or perchlorates, persulfates, percarbonates, bichromates, hydrogen peroxide or other suitable oxidizing materials may be used to impregnate the active carbon, the amount in general being about of the weight of the carbon. This prepared oxidizing catalytic material is then placed while still Wet into the nickel screen basket 40 and after the container 39 has been substantially filled with the material to be treated, the neon tube is operated and the oxidizing treatment carried on until the desired amount of the desired alcohol is formed. As indicated above, when treating complex hydrocarbons, a degradation tends to occur simultaneously with the formation of alcohol or ketones.

For producing ethyl alcohol from gasoline,

for example, I have found it desirable to use a neon tube (e. g. 1l mm. outside diameter) with an impressed voltage of about 1,000 volts and a tube current of about 4 milliamperes, `,the treatment being carried on for from about 24 to 36 hours in the apparatus shown in Fig. '7, but without the member 46. 5

For treating more complex hydrocarbons such as kerosene, the treatment is in general the Same, but the amperage or time of treatment is suitably increased and, as will be apparent to one skilled in the art, if larger capacity tubes or higher impressed voltages are used the amperage and time of treatment are varied according to the results desired.

For the production of alcohols the neon tube may, if desired, be replaced by an argon tube.

For treating hydrocarbons for depolymerization, the voltages and times of treatment may vary widely but in general I have found somewhat higher voltages say around '7,000 to 15,000 volts to give good results.

Another suitable oxidizing catalytic material can be formed, using pumice stone as a carrying material, by soaking cracked pumice stone in a copper sulphate solution; adding sufficient sodium hydroxide until the re-solution of the copper hydroxide has not quite commenced (that is, until a blue precipitate is formed, as distinguished from the initially formed green precipitate); then adding a small amount of sodium bicarbonate solution to throw back the precipitation slightly and to give a gelatinous ,mixture containing about 1 to 2% of copper sulphat admixed with some copper carbonate and copper hydroxide, so that the precipitate.

has approximately a neutral reaction and the liquid is slightly acid. In order to get this catalytic material in the most active form, the treatment must be carried out at a temperature suliiciently low to prevent the formation of a black precipitate, and I have found a temown water of crystallization such as, for example, the sulphocyanates. Active carbon may be impregnated with these materials, preferably in colloidal form by the use of agar-agar in the* same manner as described above in connection with the oxidizing type of catalytic material and are also used in a wet state.

Another suitable form 'of reducing catalytic material may be prepared by thoroughly cleaning aluminum filings, as by dipping them for a moment into a solution (e. g. about of sodium hydroxide; quickly washing with distilled water; then dipping into a solution of mercurio chloride (e. g. about 0.5%) washing with water and covering the prepared aluminum with benzol or the like to exclude the air until it is used. A several times repetition of the treatment is found to improve the catalytic material.

A suitable material for use in the lter bed 26 shown in Fig. 3, in the degradation of complex aliphatic hydrocarbons, may be prepared by dipping pumice stone in the copper hydroxide precipitate formed as above described; then placing it in a Gooch Crucible or the like; washing out the electrolyte; heating to about 130 C., to form black copper oxide; and nally placing the Crucible over methyl alcohol whereby the copper oxide is reduced to a spongy form of metallic copper. 'I'his copper impregnated pumice stone is susceptible to oxidation and hence after preparation should be kept away from air as, for example, by covering with benzol or the like, until it is used. When thus prepared the pumice stone will carry about 6 to '1%.

of copper.

This copper impregnated pumice stone may also conveniently be used in place of active carbon as a carrier for the chemical oxidizing or reducing substances referred to above to form an oxidizing or reducing catalytic material. A similarly active impregnated pumice base can be prepared by soaking cracked pumice stone in a solution of nickel nitrate; adding sodium hydroxide solution to form a precipitate of nickel hydroxide; removing the pumice stone from the solution, washing out the electrolyte; and heating to about 300`C. Such nickel oxide impregnated pumice may be used in a like manner and for like purposes, as the copper impregnated pumice referred to above.

By the treatment of aliphatic hydrocarbon compounds in the presence of oxidizing catalytic materials of the type described, with a rare gas tube such as neon, I havel found it possible, for example, to convert kerosene directly into ethyl, butyl, and amyl alcohols, and by using the reducing catalyzing materials I have been able to form the corresponding ketones.

It will thus be seen that by means of the present invention novel means and processes have been developed whereby aliphatic hydrocarbon compounds may be degraded, oxidized or reduced as desired, and since certain changes in carrying out the above process and in the construction set forth, which embody the invention may be made without departing from its scope, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. Particularly it is to be understood that in said claims ingredients recited in the singular are intended to include mixtures of such ingredients wherever the sense permits.

It is also to be understood that the following claims are intended to cover all of the generic and specic features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.

Having described my invention, what I claim as new and desire to secure by Letters Patent, is:

1. A process of degrading a hydrocarbon 1 which comprises exposing said hydrocarbon to bon to the action of a positive column neo'n lamp until it is degraded.

4. A continuous process of degrading an aliphatic hydrocarbon which comprises passing said hydrocarbon continuously Vover a positive column rare gas lamp at a rate such that the hydrocarbon is degraded.

5. A continuous process of degrading an ali-V phatic hydrocarbon which comprises passing said hydrocarbon continuously over a positive column neon lamp operating under a potential of '7,000 to 15,000 volts, at a temperature above atmospheric and ata rate such that the hydrocarbon is degraded. f

6. A continuous process of degrading an aliphatic hydrocarbon which comprises passing said hydrocarbon continuously in the vapor form over a positive column rare gas lamp operating at a potential upwards to 15,000 volts, at a temperature above atmospheric and at a rate such that the hydrocarbon is degraded.

`7. A continuous process of degrading an aliphatic hydrocarbon which comprises passing said hydrocarbon continuously in vapor form overa positive column neonlamp operating at a potential upwards to 15,000 volts, at a temperature above atmospheric and at a rate such that the hydrocarbon is degraded. 8. A process of degrading an aliphatic hydrocarbonv which comprises subjecting a' heated mixture of said` hydrocarbon and water to the action of a positive column rare gas'lamp operating at a potential upwards of 15,000 volts, and at a temperaturel upwards to 400 C., until the hydrocarbon is degraded.

9. A process of degrading an aliphatic hydrocarbon which comprises subjecting a Treated mixture of said hydrocarbon and water to the action of a positive column neon lamp operating at a potential upwards of 15,000 volts, and at a temperature upwards to 400 C., `until the hydrocarbon is degraded.

10. A continuous process of degrading 'an aliphatic hydrocarbon which comprises passing a heated mixture of said hydrocarbon and water both in vapor form continuously over a positive column rare gas lamp operating at a potentialupwardsof 15,000 volts, and at a temperature upwards to 400 C., at a rate such thatY said hydrocarbon is degraded.

11. A continuous process of degrading an aliphatic hydrocarbon which comprises passing a heated mixture of said hydrocarbon and water both invapor form continuously over a positive column neon lamp operating at apotential upwards of 15,000volts, and a temperature upwards to 400 C., at a rate such that said hydrocarbon is degraded.

12. A continuous processv of degrading an aliphatic hydrocarbon which comprises vpassing a heated mixture of said hydrocarbon and water both in vapor form continuously over ak positive column rare gas lamp operating at a potential upwards of 15,000 volts, and at a temperature upwards to 400 C., at a rate such that said hydrocarbon is degraded, and under a partial vacuum.

13. A continuous process of degrading an aliphatic hydrocarbon` which comprises passing a heated mixture of said hydrocarbon and Water both in vapor form continuously over a positive column neon lamp operating at a potentialupwards ofy 15,000 Volts, and at a temperature upwards to 400 C., at a rate such that said hydrocarbon is degraded, and under a partial vacuum.

14. A' continuous process of degrading an aliphatic hydrocarbon which comprises passing a heated mixture of said hydrocarbon and wa.- ter `both in vapor form continuously over a positive column raregas lamp operating ata potential upwards of 15,000 volts, and at a temperature upwards to 400 C., at a rate such that said hydrocarbon is degraded, and under a pressure vof about 200 mm. mercury.

15. A process on converting an aliphatic Vhydrocarbon into an oxygenated compound which comprises subjecting said hydrocarbon in the presence of a catalytic material containing a per-compound belonging to the group consisting of a perborate, a persulfate, a percarbonate, a bichromate and hydrogen peroxide to the action of radiations from a rare gas lamp operating at a potential upwards of 1,000 volts at about atmospheric temperature and for a period suiicient to effect conversion.

16. A process of converting an aliphatic hydrocarbon into an alcohol which comprises subjecting said hydrocarbon in the presence of water and an oxidizing catalytic material con-A taining a per-compound belonging to the group consisting of a perborate, a persulfate, a percarbonate, a bichromate and hydrogen peroxide to the action of a positive column rare gas lamp operating at a potential upwards of 1,000 volts at about atmospheric temperature and for a period sucient to eiect conversion.

i 17. A process of converting an aliphatic hydrocarbon into an alcohol which comprises subjecting said hydrocarbon in the presence of water and an oxidizing catalytic material containing a per-compound belonging to the group consistingV of a perborate, a persulfate, a percarbonate, a bichromate and hydrogen peroxide to the action of a positive column neon lamp operating at a potential upwards of 1,000 volts at about atmospheric temperature and for a period sufficient to effect conversion.

18. A process of converting an aliphatic hydrocarbon into an alcohol which comprises subjecting said hydrocarbon in the presence of water and an oxidizing catalytic materialto the action of a positive column neon lamp operating at a potential upward of l1,000 volts at about atmospheric temperature and for a period sutlicient to effect conversion, said catalytic material being composed oi an insoluble granular porous substance impregnated with a percompound belonging to the group consisting of a perborate, a persulfate, a percarbonate, a 'bichromate and hydrogen peroxide.

19. A process of converting an aliphatic hydrocarbon into an alcohol which comprises subjectingsaid hydrocarbon in the presence of water and an oxidizing catalytic material to the action of a positive column neon lamp operating at a potential upwards of 1,000 volts at about atmospheric temperature and for a period suflicient to eiect conversion, said catalytic material being composed of active carbon impregnated with a per-compound belonging to the group consisting of a perborate, a persulfate, a percarbonate,

'a bichromate and hydrogen peroxide.

20. A process of converting an aliphatic hydrocarbon into an alcohol which comprises subjecting said hydrocarbon in the presence of water and an oxidizing catalytic material to the action of a positive column neon lamp operating at a potential upwards of 1,000 volts at about atmospheric temperature and for a period suicient to eiect conversion, said catalytic material being composed of granular active carbon impregnated with a per-compound belonging to the group consisting of a perborate, a

Ypersulfate, a percarbonate, a bichromate and hydrogen peroxide in a colloidal state.

21. A process of converting an aliphatic hydrocarbon into an alcohol which comprises subjecting said hydrocarbon in the presence of water and an oxidizing catalytic material to the action of a positive column neon lamp operating at a potential upwards of 1,000 volts at about atmospheric temperature and for a period suiicient to eiect conversion, said catalytic material being composed of granular active carbon impregnated with a colloidal mixture of a material of the empirical class consisting of agar-agar, gum arabic, glue and glucose and with an oxidizing agent of the empirical class consisting of a perborate, a perchlorate, a persulfate, a percarbonate, a bichromate, and hydrogen peroxide.

22. A process of converting an aliphatic hydrocarbon into an alcohol which comprises subjecting said hydrocarbon in the presence of water and an oxidizing catalytic material to the action of a positive column neon lamp, said catalytic material being composed of an insoluble porous substance impregnated with a mixture of copper hydroxide, copper carbonate and a smallV amount of copper sulphate.

2 3. A process of 1 converting an aliphatic hydrocarbon into an alcohol which comprises subjecting said hydrocarbon in the presence of water and an oxidizing catalytic material to the action of a positive column neon lamp, said catalytic material being composed of broken pumice stone impregnated with a colloidal mixture of copper hydroxide, copper ycarbonate and a small amount of copper sulphate.

24. A process of converting an aliphatic hydrocarbon into an alcohol which comprises subjecting said hydrocarbon in the presence of water and an voxidizing catalytic material to the action of a positive column neon lamp, said catalytic material being composed of metallized broken pumice stone impregnated with a colloidal mixture of copper hydroxide, copper carbonate anda small amount of copper sulphate.

25. Asprocess of converting an aliphatic hydrocarbon into an alcohol which comprises subjecting said hydrocarbon in the presence of water andan oxidizing catalytic material to the action of.apositive column neon lamp, said catalytic ymaterial being composed of metallized broken pumice stone impregnated with a co1- loidal mixture of copper hydroxide, copper carbonate and a small amount of copper sulphate, said metallized pumice stone being prepared by depositing thereon a mixture of copper hydroxide, copper carbonate and a small amount of copper sulphate, thereafter heating the mass-v to produce copper oxide, and while hot reducing the copper oxide by treatment with methyl alcohol vapor; the metallized pumice stone being subsequently impregnated. 26. A process of converting an aliphatic hydrocarbon into an alcohol which comprises-sub-4 jecting said hydrocarbon in the presence of water ,and an oxidizing catalytic material to the action of a positive column neon lamp, said catalytic material being composed of metallized broken pumice stone prepared impregnating with a colloidal mixture of copper hydroxide, copper carbonate and a small amount of copper sulphate and subsequently reducing to metallic copper, impregnated with an oxidizing material of the empirical class consisting of a perborate, a perchlorate, a persulfate, a percarbonate, a bichromate and hydrogen peroxide.

27. A catalytic material for the conversion of an aliphatic hydrocarbon into an oxygenated compound consisting of an insoluble porous substance impregnated with a per-compound belonging to the group consisting of a perborate, a persulfate, a percarbonate, a bichromate and hydrogen peroxide.

28. A catalytic material for the conversion of an aliphatic hydrocarbon into an oxygenated compound consisting of a granular active carbon impregnated with a per-compound belonging to the group consisting of a perborate, a persulfate, a percarbonate, a bichromate and hydrogen peroxide in a colloidal state.

29. A catalytic material for the conversion of an aliphatic hydrocarbon into an oxygenated compound consisting of a granular active carbon impregnated with a colloidal mixture containing an oxidizing agent of the class consisting of a perborate, a perchlorate, a persulfate, a percarbonate, a bichromate and `hydrogen peroxide.

30. A catalytic material for the conversion of an aliphatic hydrocarbon into an oxygenated compound consisting of an insoluble granular porous substance impregnated with a mixture of, copper hydroxide, copper` Carbonate and a vsmally amount of copper sulphate. 1

an aliphatic hydrocarbon vinto an oxygenated compound consisting of metallized pumice stone impregnated with a colloidal mixture of copper hydroxide, copper carbonate and a small amount of copper sulphate. Y

32. A catalytic material for the conversion of 31. A catalytic material for the conversion of i an aliphatic hydrocarbon into an oxygenatedA compound consisting of metallized pumice stone, prepared by impregnating with a colloidal mixture of copper hydroxide', copper carbonate and ya small amount of copper sulphate and subsequently reducing to metallic copper, and impregnated with a substance of the class consisting of a perborate, a perchlorate, a persulfate, a percarbonate, a bichromate and hydrogen peroxide.

33. A catalytic material for the conversion of y .assembling desired ingredients including a hysion of hydrocarbons the step which comprises drocarbon in the presence of a. catalyst containing a. per-compound belonging to the class consisting of a perborate, a percarbonate, a bichromate and hydrogen peroxide and under the influence of radiations from a positive column rare gas tube.

WALDEMAR O. MITSCHERLINGL 

